CN107585843A - Ecological restoration material and its preparation method and application - Google Patents
Ecological restoration material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of ecological restoration material and its preparation method and application.A kind of preparation method of ecological restoration material, comprises the following steps：Cladding reagent, iron particle and organic solvent are mixed and are ultrasonically treated, cladding reagent is coated in iron particle and form clad, obtain mixture, wherein, cladding reagent is selected from least one of stearic acid and odium stearate, and the mass ratio for coating reagent and iron particle is 0.1~2:100, the particle diameter of iron particle is 1 nanometer~100 nanometers；Mixture is heating and curing, obtains ecological restoration material.The dispersiveness for the ecological restoration material that the preparation method of above-mentioned ecological restoration material is prepared is preferably and antioxygenic property is preferable.
Description
Technical field
The present invention relates to depollution of environment process field, more particularly to a kind of ecological restoration material and preparation method thereof and should
With.
Background technology
Nano zero valence iron (Nanoscale Zero-valent Iron, NZVI) refers to the iron that particle diameter is 1~100nm
Grain, have the characteristics that specific surface area greatly, strong reducing property.Nano zero valence iron not only has superior absorption property and very high reduction
Activity, its distinctive skin effect and small-size effect, the reactivity and treatment effeciency of zero-valent iron particle can also be improved.Just
Because some new features not possessed with traditional material, the research of nano zero valence iron turns into the forward position focus studied now.
Largely scientific investigations showed that nano zero valence iron can remove a variety of environment such as removing heavy metals, organic matter and inorganic matter extensively
Pollutant.But because nano zero valence iron has magnetic, and particle is small, specific surface area is big, surface energy is high and causes nano zero valence iron
Easily reunite, exposure is easily oxidized in atmosphere so that reactivity is relatively low, in actual applications by a definite limitation.
The content of the invention
Based on this, it is necessary to which the dispersed preferable and preferable environment remediation of antioxygenic property can be prepared by providing one kind
The preparation method of material.
In addition, also provide a kind of ecological restoration material and its application.
A kind of preparation method of ecological restoration material, comprises the following steps：
Cladding reagent, iron particle and organic solvent mixing are carried out into supersound process makes the cladding reagent be coated on the iron
Clad is formed on particle, obtains mixture, wherein, it is described cladding reagent in stearic acid and odium stearate at least one
Kind, the mass ratio of the cladding reagent and the iron particle is 0.1~2:100, the particle diameter of the iron particle is 1 nanometer~100
Nanometer；And
The mixture is heating and curing, obtains ecological restoration material.
Stearic acid, the odium stearate energy in the air of normal temperature and pressure used in the preparation method of above-mentioned ecological restoration material
Enough stable presence, be coated on nano iron particles and coat the clads of nano iron particles to be formed, can effectively every
Exhausted iron contacts with oxygen, so as to improve the oxidation resistance of ecological restoration material；Simultaneously as stearic acid or odium stearate bag
The presence of coating, the distance between nano iron particles is increased, and reduce the electrostatic magnetic force between nano iron particles, so that on
Stating ecological restoration material has preferable dispersive property, therefore, above-mentioned ecological restoration material have concurrently preferable oxidation resistance and
Dispersiveness.
In one of the embodiments, the thickness of the clad is 0.5 nanometer~5 nanometers.
In one of the embodiments, it is described to mix cladding reagent, iron particle and organic solvent, and be ultrasonically treated
The step of be specially：The cladding reagent is dissolved in the organic solvent, obtains premixed liquid；By the iron particle with it is described
Premixed liquid mixing is ultrasonically treated.
In one of the embodiments, the one kind of the organic solvent in methanol and ethanol, it is described by the cladding
Reagent is dissolved in the step in the organic solvent, and solution temperature is no more than 60 DEG C.
In one of the embodiments, the time of the supersound process is 10 minutes~30 minutes.
In one of the embodiments, the organic solvent and the volume mass ratio of the iron particle are 5 milliliters~10 millis
Rise:1 gram.
In one of the embodiments, the cladding reagent is stearic acid, the step that the mixture is heating and curing
In rapid, the temperature that is heating and curing is no more than 55 DEG C；It is described to heat the mixture or the cladding reagent is odium stearate
In the step of solidification, the temperature that is heating and curing is no more than 150 DEG C.
In one of the embodiments, the preparation process of the iron particle is included：
Mixed liquor containing ferrous ion, boron hydride and water is subjected to reduction reaction, obtains reaction solution；And
By the reacting liquid filtering, the iron particle is obtained.
The ecological restoration material that the preparation method of above-mentioned ecological restoration material is prepared.
Application of the above-mentioned ecological restoration material in the purified treatment of sewage or the purified treatment of soil.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the ecological restoration material of an embodiment；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of Nanoscale Iron prepared by the step 2 of embodiment 1；
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the ecological restoration material of embodiment 1；
Fig. 4 is curve map (its that the Nanoscale Iron of embodiment 1 and ecological restoration material change with time to the clearance of lead
In, A lines are the Nanoscale Iron without cladding, and B lines are ecological restoration material)；
Fig. 5 is the scanning electron microscope (SEM) photograph (SEM) of the ecological restoration material of embodiment 3；
Fig. 6 is curve map (its that the Nanoscale Iron of embodiment 3 and ecological restoration material change with time to the clearance of lead
In, C lines are the Nanoscale Iron without cladding, and D lines are ecological restoration material).
Embodiment
For the ease of understanding the present invention, the present invention is described more fully below with reference to relevant drawings.In accompanying drawing
Give the preferred embodiment of the present invention.But the present invention can realize in many different forms, however it is not limited to herein
Described embodiment.On the contrary, the purpose for providing these embodiments is to make the understanding to the disclosure more saturating
It is thorough comprehensive.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
As shown in figure 1, the preparation method of the ecological restoration material of an embodiment, comprises the following steps：
Step S110：Cladding reagent, iron particle and organic solvent are mixed and are ultrasonically treated, is coated on cladding reagent
Clad is formed in iron particle, obtains mixture.
Wherein, the frequency of supersound process is between 20kHz~1300kHz.
Wherein, cladding reagent is selected from least one of stearic acid and odium stearate.Because two kinds of materials are in water
Solubility is small, and dissolving is slow, has good slow release, and two kinds of materials can be absorbed by the micro-organisms.
Wherein, the mass ratio for coating reagent and iron particle is 0.1~2:100.
Wherein, the particle diameter of iron particle be 1 nanometer~100 nanometers, as nano zero valence iron.
Wherein, organic solvent is that physico-chemical property is relatively stable and nontoxic organic matter；Specifically, organic solvent is selected from methanol
And at least one of ethanol.Methanol and ethanol will not react with reactant, according to the organic solvent of other macromoleculars
Easily acted on reactant, be unfavorable for the preparation of ecological restoration material.
Wherein, organic solvent and the volume mass of iron particle ratio are 5 milliliters~10 milliliters:1 gram.The dosage meeting of organic solvent
The volume mass of the coating thickness of influence iron particle, the organic solvent and iron particle is than that can make the clad in iron particle
Thickness reaches 0.5 nanometer~5 nanometers.
Specifically, the step of cladding reagent, iron particle and organic solvent being mixed, then being ultrasonically treated be specially：Will
Coat reagent dissolving in organic solvent, obtain premixed liquid；Iron particle is mixed with premixed liquid, and is ultrasonically treated.
Wherein, in the step of cladding reagent being dissolved in organic solvent, solution temperature is no more than 60 DEG C, secondary anti-to prevent
The generation answered and the volatilization loss of reduction organic solvent；Further, solution temperature is 50 DEG C~60 DEG C.
Wherein, the time of supersound process is 10 minutes~30 minutes.
Wherein, iron particle can be prepared into by the methods of liquid phase reduction, gas-phase chemical reduction method, gas phase thermal decomposition method
Arrive.In the present embodiment, the preparation process of iron particle is as follows：Ferrous ion will be contained, boron hydride is reduced in water
Reaction, obtains reaction solution；By reacting liquid filtering, iron particle is obtained.
Wherein, ferrous ion can be provided by way of the compound containing ferrous ion, such as ferrous sulfate, chlorine
Change ferrous iron etc.；Boron hydride is at least one of sodium borohydride and potassium borohydride.Wherein, boron hydride and ferrous ion
Mol ratio is 0.05~0.2:0.05.
Wherein, the thickness of clad is 0.5 nanometer~5 nanometers.
Because solubility of the stearic acid in aqueous phase is smaller, when the clad that the stearic acid on the surface of Nanoscale Iron is formed is thicker
When, stearic acid solubility in water is small, and clad is only partly dissolved, and remainder does not dissolve, and repair materials may be caused to lose
Lose its inherent function or its effect can not be played；Because the grain diameter of ecological restoration material is smaller, surface tension is big, can float on
The water surface, and stearic acid is readily soluble in the lightweight nonaqueous phase liquid to float on the surface, therefore, can increase above-mentioned ring when clad is thicker
Border repair materials improve ecological restoration material in water table aquifer to the contact rate of lightweight nonaqueous phase liquid organic pollution
Lightweight nonaqueous phase liquid organic pollution degradation property.And odium stearate is to the rush of Nanoscale Iron degraded lightweight nonaqueous phase liquid
It is similar with above-mentioned stearic facilitation to enter effect.And by controlling the thickness of clad to make for 0.5 nanometer~5 nanometers
Above-mentioned ecological restoration material lifts common Nanoscale Iron to organic pollutants (dyestuff, Polychlorinated biphenyls, persistence organic pollutant
Deng pollutant), the degradation property of heavy metal, further increase to lightweight nonaqueous phase liquid (LNAPLs), such as float on the surface
Lipid, ketone, aldehydes etc., the degradation property of the organic pollution of the lightweight nonaqueous phase liquid particularly in shoaling layer.
Further, since odium stearate can hydrolyze in water and be in alkalescence, and the activity of Nanoscale Iron is more preferable under alkaline environment,
Nanoscale Iron can be promoted to carry out reaction and generate more hydroxyl radical free radicals, and then strengthen ecological restoration material to lightweight nonaqueous phase liquid
The degradation property of body organic pollution.Above-mentioned ecological restoration material can also greatly lift common Nanoscale Iron to organic dirt in water
Contaminate thing (pollutant such as dyestuff, Polychlorinated biphenyls, persistence organic pollutant), the degradation property of heavy metal, further increase pair
Lightweight nonaqueous phase liquid (LNAPLs), the lipid such as to float on the surface, ketone, aldehydes, the lightweight particularly in water table aquifer
The degradation property of the organic pollution of nonaqueous phase liquid.
Step S120：Mixture is heating and curing, obtains ecological restoration material.
By the way that mixture is heating and curing to remove organic solvent, and solidify mixture.
Wherein, when it is stearic acid to coat reagent, in the step of mixture is heating and curing, the temperature that is heating and curing is no more than
55℃；It is odium stearate or during containing odium stearate when coating reagent, in the step of mixture is heating and curing, is heating and curing
Temperature is no more than 150 DEG C.To prevent the too high clad of temperature from decomposing, and nano zero valence iron is prevented to be oxidized.
Specifically, the step of mixture being heating and curing be：Air blast curing process 1 hour~2 is small at 30 DEG C~55 DEG C
When.
Stearic acid, the odium stearate energy in the air of normal temperature and pressure used in the preparation method of above-mentioned ecological restoration material
Enough stable presence, be coated on nano iron particles and coat the clads of nano iron particles to be formed, can effectively every
Exhausted iron contacts with oxygen, so as to improve the oxidation resistance of ecological restoration material；Simultaneously as stearic acid or odium stearate bag
The presence of coating, increase the distance between nano iron particles and reduce the electrostatic magnetic force between nano iron particles, so that on
Stating ecological restoration material has preferable dispersive property, therefore, above-mentioned ecological restoration material have concurrently preferable oxidation resistance and
Dispersiveness.
And the material of above-mentioned ecological restoration material can be slightly soluble in water for the clad of stearic acid or odium stearate, and it is dissolved in
Part of stearic acid or stearate radical ion in water generate insoluble with heavy metal ion reactions such as the lead in water, copper, chromium, cadmium, calcium
In the stearate of water, and then the immobilization of heavy metal, stabilized purpose, so as to also improve ecological restoration material
Clean-up effect；And being continuously generated with stearate, stearic acid or the odium stearate for being covered in the surface of Nanoscale Iron are continuous
Ground is soluble in water, and when the stearic acid of surface covering or after odium stearate all soluble in water, not oxidized in clad is received
Rice iron starts to be reacted with heavy metal ion soluble in water, organic pollution etc., last stabilized or be degraded to small
Molecular compound (such as carbon dioxide and water), so that above-mentioned ecological restoration material embodies sustained release performance.
In addition, after the surface coated stearic acid or odium stearate of Nanoscale Iron are soluble in water, it is anti-with metal ion generation
The stearate that should be generated is also important nutrition of the microorganism in metabolic processes in soil, underground water and surface water
Source-carbon source, that is to say, that the Nanoscale Iron coated using stearic acid, odium stearate is in rehabilitating soil, underground water and earth's surface water ring
When border is polluted, promote the growth of microorganism in conversion zone to a certain extent, and microorganism and can is cooperateed with to dirt with Nanoscale Iron
Dye thing is degraded, immobilization or stabilisation, is added the reactivity of Nanoscale Iron, is improved environment of the Nanoscale Iron to pollutant
The degradation property of reparation, so that above-mentioned ecological restoration material has preferable clean-up effect.
And the preparation method of above-mentioned ecological restoration material is simple to operate, is easy to industrialized production.
The ecological restoration material of one embodiment, it is prepared by the preparation method of above-mentioned ecological restoration material, above-mentioned ring
Border repair materials have more more preferable than common Nanoscale Iron dispersiveness and inoxidizability, are a kind of iron-based environment remediation materials of spacetabs type
Material, has preferable clean-up effect to sewage and soil.
The ecological restoration material can be used in the purified treatment of sewage or the purified treatment of soil.The ecological restoration material
With it is more more preferable than common Nanoscale Iron dispersiveness and inoxidizability, be a kind of spacetabs type iron-based ecological restoration material, for dirt
In the purified treatment of water or the purified treatment of soil, preferable clean-up effect can be reached.
For embodiment part, (following examples unless otherwise specified, are not then contained in addition to inevitable impurity below
Other components for pointing out are not known.)：
Embodiment 1
The preparation process of the ecological restoration material of the present embodiment is as follows：
(1) ferrous sulfate heptahydrate of 13.9005 grams (0.05mol) is dissolved in 30 milliliters of water, forms ferrous sulfate
The aqueous solution；The sodium borohydride of 7.566 grams (0.2mol) is dissolved in 50 milliliters of water, obtains the aqueous solution of sodium borohydride.
The aqueous solution of ferrous sulfate is instilled in the aqueous solution of sodium borohydride, treat that the aqueous solution of sodium borohydride drips, obtain reaction solution.
(2) magnetic separation reaction solution obtains black particle, successively with deionized water and washes of absolute alcohol black particle, then
By black particle in vacuum drying chamber 150 DEG C of dryings 0.5 hour, obtain the iron particle that particle diameter is 10 nanometers~100 nanometers.
(3) weigh 0.01 gram of stearic acid to be placed in 10mL absolute ethyl alcohols, and be heated to 55 DEG C, make stearic acid thoroughly molten
Solution, obtains premixed liquid.
(4) Nanoscale Iron that 1 gram of step (2) is prepared is added in the premixed liquid that step (3) is prepared, in frequency
To be ultrasonically treated 20 minutes under 500kHz, so that stearic acid, which is coated in iron particle, forms clad, mixture is obtained, will be mixed
Thing air blast curing process 1.5 hours at 50 DEG C, obtain the ecological restoration material of the present embodiment, wherein, the average thickness of clad
About 1.3 nanometers of degree.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Nanoscale Iron without cladding prepared by step (2), and Fig. 3 is ring manufactured in the present embodiment
The scanning electron microscope (SEM) photograph of border repair materials, as can be seen that the Nanoscale Iron without cladding is in reunion shape bulk structure from Fig. 2 and Fig. 3,
And particle diameter is larger, and the ecological restoration material of the present embodiment is in slice dispersed, has preferably dispersiveness by contrast.
It is respectively placed in what step (2) was prepared and contains without the Nanoscale Iron of cladding and the ecological restoration material of the present embodiment
In the aqueous solution for having 200ppm concentration lead, record without the Nanoscale Iron of cladding and the ecological restoration material of the present embodiment with the time
Change to the clearance of lead, and the Nanoscale Iron and the ecological restoration material of the present embodiment not coated change with time pair
The curve map of the clearance of lead, such as Fig. 4, (wherein, A lines are expressed as the Nanoscale Iron not coated, and B lines are expressed as the ring of the present embodiment
Border repair materials), and record and the clearance of lead is reached without the Nanoscale Iron of cladding and the ecological restoration material of the present embodiment
Time when 99% is shown in Table 1.Figure 4, it is seen that the Nanoscale Iron that the present embodiment is prepared only needs 30 minutes to lead
Clearance can reach nearly 99%, and the ecological restoration material of the present embodiment needs the nearly 24 hours clearance ability to lead
Reach 99%, this clad of explanation on Nanoscale Iron can effectively postpone the release of the reactivity of Nanoscale Iron, have very
Good slow release.
The Nanoscale Iron of the step of the present embodiment is tested using salt spray test method respectively (2) preparation and resisting for ecological restoration material
Oxidation susceptibility, it is shown in Table 1.Wherein, salt spray test standard is with reference to national standard《GB/T 10125-2012 artificial atmosphere corrosion test salt fogs
Experiment》, 5% sodium chloride solution continuously sprays 12h, salt solution Ph values 6.9,35 DEG C, spray amount 2ml/h of brine temp, relative humidity
98%.
Embodiment 2
The preparation process of the ecological restoration material of the present embodiment is as follows：
(1) ferrous sulfate heptahydrate of 13.9005 grams (0.05mol) is dissolved in 30 milliliters of water, forms ferrous sulfate
The aqueous solution；The sodium borohydride of 1.8915 grams (0.05mol) is dissolved in 50 milliliters of water, obtains the water-soluble of sodium borohydride
Liquid.The aqueous solution of ferrous sulfate is instilled in the aqueous solution of sodium borohydride, treat that the aqueous solution of sodium borohydride drips, reacted
Liquid.
(2) magnetic separation reaction solution obtains black particle, successively with deionized water and washes of absolute alcohol black particle, then
By black particle in vacuum drying chamber 150 DEG C of dryings 0.5 hour, obtain the iron particle that particle diameter is 10 nanometers~100 nanometers.
(3) weigh 0.02 gram of stearic acid to be placed in 5mL absolute methanols, and be heated to 60 DEG C, stearic acid is thoroughly dissolved,
Obtain premixed liquid.
(4) Nanoscale Iron that 1 gram of step (2) is prepared is added in the premixed liquid that step (3) is prepared, in frequency
To be ultrasonically treated 10 minutes under 1300kHz, so that stearic acid, which is coated in iron particle, forms clad, mixture is obtained, will be mixed
Compound air blast curing process 1 hour at 55 DEG C, obtains the ecological restoration material of the present embodiment, wherein, the average thickness of clad
About 4.3 nanometers of degree.
It is no longer superfluous herein because the ecological restoration material of the present embodiment has the scanning electron microscope (SEM) photograph similar with embodiment 1
State.
Using the identical method of testing of embodiment 1, the Nanoscale Iron of step (2) and the environment remediation of the present embodiment are respectively obtained
Time and oxidation resistance when material reaches 99% to the clearance of lead are shown in Table 1.
Embodiment 3
The preparation process of the ecological restoration material of the present embodiment is as follows：
(1) frerrous chloride of 6.3375 grams (0.05mol) is dissolved in 30 milliliters of water, forms the water-soluble of frerrous chloride
Liquid；The sodium borohydride of 3.783 grams (0.1mol) is dissolved in 50 milliliters of water, obtains the aqueous solution of sodium borohydride.By chlorination
The ferrous aqueous solution is instilled in the aqueous solution of sodium borohydride, is treated that the aqueous solution of sodium borohydride drips, is obtained reaction solution.
(2) magnetic separation reaction solution obtains black particle, successively with deionized water and washes of absolute alcohol black particle, then
By black particle in vacuum drying chamber 150 DEG C of dryings 0.5 hour, obtain the iron particle that particle diameter is 3 nanometers~80 nanometers.
(3) odium stearate for weighing 0.05g is placed in 10mL absolute ethyl alcohols, and is heated to 55 DEG C, makes odium stearate thorough
Dissolving, obtains premixed liquid.
(4) Nanoscale Iron that 1 gram of step (2) is prepared is added in the premixed liquid that step (3) is prepared, in frequency
To be ultrasonically treated 30 minutes under 20kHz, so that odium stearate, which is coated in iron particle, forms clad, mixture is obtained, will be mixed
Compound air blast curing process 2 hours at 50 DEG C, obtain the ecological restoration material of the present embodiment, wherein, the average thickness of clad
About 4.7 nanometers of degree.Fig. 5 is the scanning electron microscope (SEM) photograph of ecological restoration material manufactured in the present embodiment, as can be seen from Figure 5 this reality
The ecological restoration material for applying example is in slice dispersed, has preferably dispersiveness.
Using the identical method of testing of embodiment 1, step (2) is obtained without the Nanoscale Iron of cladding and the environment of the present embodiment
The curve map that repair materials change with time to the clearance of lead, such as Fig. 6, (wherein, C lines are expressed as the nanometer not coated
Iron, D lines are expressed as the ecological restoration material of the present embodiment), and record and repaiied without the Nanoscale Iron of cladding and the environment of the present embodiment
Time when multiple material reaches 99% to the clearance of lead is shown in Table 1.Figure 4, it is seen that receiving of being prepared of the present embodiment
Rice iron only needs 30 minutes clearances to lead to can reach nearly 99%, and the ecological restoration material of the present embodiment needs nearly
17 hours clearances to lead can be only achieved 99%, and this clad of explanation on Nanoscale Iron can effectively postpone Nanoscale Iron
The release of reactivity, there is good slow release.
Using the identical method of testing of embodiment 1, the Nanoscale Iron of step (2) and the environment remediation of the present embodiment are respectively obtained
Time and oxidation resistance when material reaches 99% to the clearance of lead are shown in Table 1.
Embodiment 4
The preparation process of the ecological restoration material of the present embodiment is as follows：
(1) frerrous chloride of 6.3375 grams (0.05mol) is dissolved in 30 milliliters of water, forms the water-soluble of frerrous chloride
Liquid；The potassium borohydride of 10.788 grams (0.2mol) is dissolved in 50 milliliters of water, obtains the aqueous solution of potassium borohydride.By chlorination
The ferrous aqueous solution is instilled in the aqueous solution of potassium borohydride, is treated that the aqueous solution of potassium borohydride drips, is obtained reaction solution.
(2) magnetic separation reaction solution obtains black particle, successively with deionized water and washes of absolute alcohol black particle, then
By black particle in vacuum drying chamber 150 DEG C of dryings 0.5 hour, obtain the iron particle that particle diameter is 3 nanometers~80 nanometers.
(3) odium stearate for weighing 0.01g is placed in 10mL absolute ethyl alcohols, and is heated to 50 DEG C, makes odium stearate thorough
Dissolving, obtains premixed liquid.
(4) Nanoscale Iron that 10 grams of steps (2) are prepared is added in the premixed liquid that step (3) is prepared, in frequency
Rate is to be ultrasonically treated 30 minutes under 500kHz, so that odium stearate, which is coated in iron particle, forms clad, obtains mixture, will
Mixture air blast curing process 2 hours at 30 DEG C, obtain the ecological restoration material of the present embodiment, wherein, clad is averaged
Thickness is about 0.7 nanometer.
It is no longer superfluous herein because the ecological restoration material of the present embodiment has the scanning electron microscope (SEM) photograph similar with embodiment 3
State.
Using the identical method of testing of embodiment 1, the Nanoscale Iron of step (2) and the environment remediation of the present embodiment are respectively obtained
Time and oxidation resistance when material reaches 99% to the clearance of lead are shown in Table 1.
Embodiment 5
The preparation process of the ecological restoration material of the present embodiment is as follows：
(1) ferrous sulfate heptahydrate of 13.9005 grams (0.05mol) is dissolved in 30 milliliters of water, forms ferrous sulfate
The aqueous solution；The potassium borohydride of 2.697 grams (0.05mol) is dissolved in 50 milliliters of water, obtains the aqueous solution of sodium borohydride.
The aqueous solution of ferrous sulfate is instilled in the aqueous solution of potassium borohydride, treat that the aqueous solution of potassium borohydride drips, obtain reaction solution.
(2) magnetic separation reaction solution obtains black particle, successively with deionized water and washes of absolute alcohol black particle, then
By black particle in vacuum drying chamber 150 DEG C of dryings 0.5 hour, obtain the iron particle that particle diameter is 10 nanometers~100 nanometers.
(3) weigh 0.015 gram of odium stearate to be placed in 8mL absolute methanols, and be heated to 60 DEG C, make odium stearate thorough
Dissolving, obtains premixed liquid.
(4) Nanoscale Iron that 1 gram of step (2) is prepared is added in the premixed liquid that step (3) is prepared, in frequency
To be ultrasonically treated 10 minutes under 1300kHz, so that odium stearate, which is coated in iron particle, forms clad, mixture is obtained, will
Mixture air blast curing process 1 hour at 100 DEG C, obtains the ecological restoration material of the present embodiment, wherein, clad is averaged
Thickness is about 2.1 nanometers.
It is no longer superfluous herein because the ecological restoration material of the present embodiment has the scanning electron microscope (SEM) photograph similar with embodiment 3
State.
Using the identical method of testing of embodiment 1, the Nanoscale Iron of step (2) and the environment remediation of the present embodiment are respectively obtained
Time and oxidation resistance when material reaches 99% to the clearance of lead are shown in Table 1.
Embodiment 6
The preparation process of the ecological restoration material of the present embodiment is as follows：
(1) frerrous chloride of 6.3375 grams (0.05mol) is dissolved in 30 milliliters of water, forms the water-soluble of frerrous chloride
Liquid；The potassium borohydride of 5.394 grams (0.1mol) is dissolved in 50 milliliters of water, obtains the aqueous solution of potassium borohydride.By chlorination
The ferrous aqueous solution is instilled in the aqueous solution of potassium borohydride, is treated that the aqueous solution of potassium borohydride drips, is obtained reaction solution.
(2) magnetic separation reaction solution obtains black particle, successively with deionized water and washes of absolute alcohol black particle, then
By black particle in vacuum drying chamber 150 DEG C of dryings 0.5 hour, obtain the iron particle that particle diameter is 3 nanometers~80 nanometers.
(3) stearic acid for weighing 0.008g is placed in 7mL absolute ethyl alcohols, and is heated to 50 DEG C, stearic acid is thoroughly dissolved,
Obtain premixed liquid.
(4) Nanoscale Iron that 1 gram of step (2) is prepared is added in the premixed liquid that step (3) is prepared, in frequency
To be ultrasonically treated 30 minutes under 20kHz, so that stearic acid, which is coated in iron particle, forms clad, mixture is obtained, will be mixed
Thing air blast curing process 2 hours at 40 DEG C, obtain the ecological restoration material of the present embodiment, wherein, the average thickness of clad
About 1.5 nanometers.
It is no longer superfluous herein because the ecological restoration material of the present embodiment has the scanning electron microscope (SEM) photograph similar with embodiment 1
State.
Using the identical method of testing of embodiment 1, the Nanoscale Iron of step (2) and the environment remediation of the present embodiment are respectively obtained
Time and oxidation resistance when material reaches 99% to the clearance of lead are shown in Table 1.
Embodiment 7
The preparation process of the ecological restoration material of the present embodiment is as follows：
(1) ferrous sulfate heptahydrate of 13.9005 grams (0.05mol) is dissolved in 30 milliliters of water, forms ferrous sulfate
The aqueous solution；The sodium borohydride of 7.566 grams (0.2mol) is dissolved in 50 milliliters of water, obtains the aqueous solution of sodium borohydride.
The aqueous solution of ferrous sulfate is instilled in the aqueous solution of sodium borohydride, treat that the aqueous solution of sodium borohydride drips, obtain reaction solution.
(2) magnetic separation reaction solution obtains black particle, successively with deionized water and washes of absolute alcohol black particle, then
By black particle in vacuum drying chamber 150 DEG C of dryings 0.5 hour, obtain the iron particle that particle diameter is 10 nanometers~100 nanometers.
(3) the cladding reagent of 0.01 gram of weighing is placed in 10mL absolute ethyl alcohols and the mixed solution of absolute methanol is (wherein, anhydrous
The volume ratio of ethanol and absolute methanol is 1:1) in, and 55 DEG C are heated to, cladding reagent is thoroughly dissolved, obtain premixed liquid, its
In, cladding reagent is 1 by mass ratio:1 stearic acid and odium stearate composition.
(4) Nanoscale Iron that 1 gram of step (2) is prepared is added in the premixed liquid that step (3) is prepared, in frequency
To be ultrasonically treated 20 minutes under 500kHz, so that cladding reagent is coated in iron particle and forms clad, mixture is obtained, will be mixed
Compound air blast curing process 1.5 hours at 50 DEG C, obtain the ecological restoration material of the present embodiment, wherein, clad is averaged
Thickness is about 1.3 nanometers.
It is no longer superfluous herein because the ecological restoration material of the present embodiment has the scanning electron microscope (SEM) photograph similar with embodiment 1
State.
Using the identical method of testing of embodiment 1, the Nanoscale Iron of step (2) and the environment remediation of the present embodiment are respectively obtained
Time and oxidation resistance when material reaches 99% to the clearance of lead are shown in Table 1.
What table 1 represented is that the ecological restoration material of embodiment 1~7 and the Nanoscale Iron of step (2) reach to the clearance of lead
Time and oxidation resistance when 99% are shown in Table 1.
Table 1
From table 1 it follows that the Nanoscale Iron that the step of embodiment 1~7 (2) is prepared only needs 30 minutes to remove lead
Except rate can reach nearly 99%, and the ecological restoration material of embodiment 1~7 at least needs nearly 12 hours clearances to lead
99% is can be only achieved, this clad of explanation on Nanoscale Iron can effectively postpone the release of the reactivity of Nanoscale Iron, tool
There is good slow release, can ensure that Nanoscale Iron makes full use of when targetting migration in repairing ground water engineering application, and then
Validity and accuracy of the Nanoscale Iron in engineer applied are improved, although the Nanoscale Iron not wrapped up has higher efficiency,
It is that it is oxidized easily, causes reactivity to reduce, and causes its utilization rate deficiency, and the ecological restoration material of embodiment 1~7
Although efficiency reduces, its internal nano zero valence iron is not easy to be oxidized, and dispersiveness is more preferable, and reactivity is more preferable.
The Nanoscale Iron that the step of embodiment 1~7 is can also be seen that from table 1 (2) is prepared is during salt spray test
Became brown by black less than 2 hours, corrosion is obvious, i.e., is oxidized corrosion, it is clear that its oxide etch speed quickly, no
Just corrode change clearly to 2h, and the ecological restoration material of embodiment 1~7 is not still bright after salt spray test 12h
Aobvious oxidized corrosion phenomenon, illustrating the ecological restoration material of embodiment 1~7 has excellent antioxygenic property.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of ecological restoration material, it is characterised in that comprise the following steps：
Cladding reagent, iron particle and organic solvent are mixed and are ultrasonically treated, the cladding reagent is coated on the iron
Clad is formed on grain, obtains mixture, wherein, the cladding reagent is selected from least one of stearic acid and odium stearate,
The cladding reagent and the mass ratio of the iron particle are 0.1~2:100, the median of the iron particle is 1 nanometer~100
Nanometer；And
The mixture is heating and curing, obtains ecological restoration material.
2. the preparation method of ecological restoration material according to claim 1, it is characterised in that the thickness of the clad is
0.5 nanometer~5 nanometers.
3. the preparation method of ecological restoration material according to claim 1, it is characterised in that described to coat reagent, iron
Particle and organic solvent mix the step of being ultrasonically treated：The cladding reagent is dissolved in the organic solvent
In, obtain premixed liquid；The iron particle is mixed with the premixed liquid, then is ultrasonically treated.
4. the preparation method of ecological restoration material according to claim 3, it is characterised in that the organic solvent is selected from first
At least one of alcohol and ethanol, described that the cladding reagent is dissolved in the step in the organic solvent, solution temperature
No more than 60 DEG C.
5. the preparation method of ecological restoration material according to claim 1, it is characterised in that the time of the supersound process
For 10 minutes~30 minutes.
6. the preparation method of ecological restoration material according to claim 1, it is characterised in that the organic solvent with it is described
The volume mass ratio of iron particle is 5 milliliters~10 milliliters:1 gram.
7. the preparation method of ecological restoration material according to claim 1, it is characterised in that the cladding reagent is tristearin
Acid, in the described the step of mixture is heating and curing, the temperature that is heating and curing is no more than 55 DEG C；Or the cladding reagent
For odium stearate, in the described the step of mixture is heating and curing, the temperature that is heating and curing is no more than 150 DEG C.
8. the preparation method of ecological restoration material according to claim 1, it is characterised in that also including the iron particle
Preparation process：
Mixed liquor containing ferrous ion, boron hydride and water is subjected to reduction reaction, obtains reaction solution；And
By the reacting liquid filtering, the iron particle is obtained.
9. the environment remediation material that the preparation method of the ecological restoration material as described in claim 1~8 any one is prepared
Material.
10. application of the ecological restoration material as claimed in claim 9 in the purified treatment of sewage or the purified treatment of soil.
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| CN112010620A (en) * | 2020-08-25 | 2020-12-01 | 上海市政工程设计研究总院（集团）有限公司 | Hydrophobic self-protection type mineral self-repairing material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006076860A (en) * | 2004-09-13 | 2006-03-23 | Tdk Corp | Method of manufacturing oxide sintered compact and composition |
| CN103050211A (en) * | 2012-12-31 | 2013-04-17 | 江苏理工学院 | Organic magnetic composite material and preparing method thereof |
| CN103623782A (en) * | 2012-08-21 | 2014-03-12 | 北京有色金属研究总院 | Preparation method for composite magnetic adsorption material and method for removing heavy metal ions in waste water |
| CN104773766A (en) * | 2015-03-23 | 2015-07-15 | 吉林大学 | Soybean oil coated nano-iron slurry groundwater pollution remediation reagent and preparation method thereof |
| CN104888689A (en) * | 2015-07-03 | 2015-09-09 | 武汉工程大学 | Preparation method of modified iron-based adsorbing material |
-
2017
- 2017-09-08 CN CN201710805581.XA patent/CN107585843B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006076860A (en) * | 2004-09-13 | 2006-03-23 | Tdk Corp | Method of manufacturing oxide sintered compact and composition |
| CN103623782A (en) * | 2012-08-21 | 2014-03-12 | 北京有色金属研究总院 | Preparation method for composite magnetic adsorption material and method for removing heavy metal ions in waste water |
| CN103050211A (en) * | 2012-12-31 | 2013-04-17 | 江苏理工学院 | Organic magnetic composite material and preparing method thereof |
| CN104773766A (en) * | 2015-03-23 | 2015-07-15 | 吉林大学 | Soybean oil coated nano-iron slurry groundwater pollution remediation reagent and preparation method thereof |
| CN104888689A (en) * | 2015-07-03 | 2015-09-09 | 武汉工程大学 | Preparation method of modified iron-based adsorbing material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010620A (en) * | 2020-08-25 | 2020-12-01 | 上海市政工程设计研究总院（集团）有限公司 | Hydrophobic self-protection type mineral self-repairing material and preparation method thereof |
| CN112010620B (en) * | 2020-08-25 | 2023-02-10 | 上海市政工程设计研究总院（集团）有限公司 | Hydrophobic self-protection type mineral self-repairing material and preparation method thereof |
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